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At least 19 records

Intermediate Temperature Single Component Electrolysis Cell

This project aims at demonstrating a fundamentally new approach towards electrochemical hydrogen production using a single component cell design. Conventional electrolyzer cells consist of a stack of layers (oxygen and fuel electrodes, electrolyte layer) that require multiple processing steps and add to the fabrication cost and complexity. Here we explore the viability of a single-layer electrolyzer device based on the single-layer SOFC concepts described in literature (Asghar et al, 2020). The single layer material is a composite of ionic conductor and catalytic material consisting of ceria doped with Gd and Sm co-processed with CuFe 2 O 4 .

08 HYDROGEN↗

Proton-Conducting Solid Oxide Electrolysis Cells for Large-scale Hydrogen Production at Intermediate Temperatures

Proton-conducting electrolyte based SOECs offer potential for operation at low to intermediate temperatures. Although yttrium-doped barium zirconate (BZY) and ceria-doped barium zirconate (BCY) have conductivity of 0.01 and 0.017 S.cm -1 respectively at 650C in comparison to the conductivity of 0.015 S.cm -1 for 8-YSZ at 850°C, there remains technology gaps and research needs related to understanding of chemical and structural stability in oxidizing and/or reducing atmospheres at intermediate temperatures, material processing and densification techniques, high polarization losses, and electrode poisoning due to intrinsic and extrinsic gas phase contaminants. Synthesis methods have produced proton-conducting materials and cells that met degradation rate targets, showcasing stable hydrogen production. Improved performance was evident in the HSOEC cell, achieving higher hydrogen production at a lower operating temperature compared to standard cells. Collaborations with multiple research facilities ensured scaling up of synthesis processes and milestone achievements for large-scale manufacturing. Assessment of contaminants revealed their adverse effects on electrode performance and structural stability. Contaminants like Cr and Si compounds, in high humidity, degraded electrodes by forming stable silicate and chromates, inhibiting active surface reactions. Getter materials showed promise in capturing contaminants, suggesting potential for mitigation.

08 HYDROGEN↗

Intermediate Temperature Proton‐Conducting Solid Oxide Electrolysis Cells with Improved Performance and Durability

Technical understanding: A high-performance and stable intermediate temperature proton-conducting solid oxide electrolysis cell (PCEC) will add significantly to the hydrogen roadmap of EERE. However, the low electrocatalytic activity of the air electrode and the instability of the electrolyte are technical barriers. In this research, we utilized computational fluid dynamic modeling and materials/microstructure engineering to investigate the complex reaction chain and to improve the performance and reliability of the protonic ceramic electrochemical cells. An active and stable Pr 1.8 Ba 0.2 NiO 4+δ -BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) scaffold conformal coating electrode was rationally designed where the robust Pr 1.8 Ba 0.2 NiO 4+δ functions both as a catalytic active and a protective layer. The PCECs with porosity-optimized scaffold conformal coating electrodes demonstrate 1.46 Acm -2 under 1.3 V at 600°C, which is among the highest in recent years. The final optimization by computational fluid dynamic modeling and conformal coating technique was applied to evolve the PCEC air electrode from Pr 2 NiO 4+δ to Pr 1.8 Ba 0.2 NiO 4+δ -BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ scaffold conformal coating. The electrolysis current was boosted from 0.445A/cm 2 to 1.46A/cm 2 at 600°C and 1.3V. A superior low degradation rate of 1mV/kh was achieved in a 5000-hour of operation. Technical effectiveness and economic feasibility: The effectiveness of this TCO conformal coating on electrolyte backbone as air electrode has been proven by long-term demonstration. Based on the highly conductive BZCYYb electrolyte and the TCO steam electrode PNO, this project rationally took advantage of the existent materials to structure a PCEC device with high TRL and low risk. The solution infiltration method used to structure the conformal coating is a standard method used by the solid oxide cell community. Very minimal adoption is needed in the current SOC fabrication process. It is a cost-effective, scalable method for manufacturing, and brings up remarkable impact on the current technical status of PCEC. Benefit to the public: The findings in the research showed the industry that the severe challenge in PCEC can be overcome in a practical way. A various energy-hydrogen ecosystem is not beyond reach. The success of this technology provides sustainable and affordable H 2 to society. It will stimulate investment from the governmental and private sectors in response to the device manufacture and deployment, and the related infrastructure construction. It will generate high-pay domestic jobs and environmental benefits to the general public in the United States.

08 HYDROGEN↗

Stability of ceramic matrix materials in molten hydroxide under oxidizing and reducing conditions

The degradation mechanism of ceramic matrix materials used as molten hydroxide electrolyte support for steam electrolysis cells, is not well documented. In this study, we have investigated the structural and chemical stability of non-oxide and oxide ceramics (SiC, YSZ, Li 2 ZrO 3, LiAlO 2 , and SrZrO 3 ) in the presence of molten hydroxide under oxidizing and reducing conditions with humidity levels of 3 and 85% at 550 °C. SiC, YSZ, Li 2 ZrO 3 and LiAlO 2 showed structural and chemical changes due to dissolution of the ceramic particles in the hydroxide melt followed by precipitation. The SrZrO 3 powder, on the other hand, remained both chemically and structurally stable during 500 h test under both oxidizing and reducing atmospheres. The findings of a stable ceramic matrix in molten hydroxide contribute to the enhancement of the durability and performance of intermediate temperature water electrolysis system.

08 HYDROGEN↗

Critical insights into the steam electrolysis electrode in protonic ceramic cells for hydrogen production

Intermediate-temperature protonic ceramic electrolysis cells (PCECs), which combine the benefits of both lower- and higher-temperature electrolysis, are among the most efficient technologies for the production of green hydrogen. To ensure economic competitiveness and broad adoption, ongoing innovations in cell materials are essential to improve durability and reduce costs. The water oxidation half-reaction at the anode is a key area for improvement as it is a major contributor to performance degradation and efficiency loss in PCECs. Current anode designs, which are largely derived from solid oxide electrolysis cells, fail to address the specific requirements for PCECs under realistic operating conditions. Here, this Perspective highlights the unique challenges faced by PCEC anodes, focusing on the impact of high steam concentrations and the critical role of proton-coupled electron-transfer mechanisms—factors that are absent in solid oxide electrolysis cells. Furthermore, we explore design principles for advancing anodes tailored for PCECs, offering guidance for future research and development in this promising field.

Electrocatalysis↗

Probing the proton exchange kinetics of BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3− δ ceramic electrolyte by operando diffuse reflectance infrared Fourier transform spectroscopy

Proton exchange kinetics plays an important role in governing the performance of intermediate-temperature protonic ceramic electrolysis cells (PCECs) for hydrogen production. Our understanding of the nature of the surface hydration reaction at the single-cell level, however, remains very limited, hampering further efficiency improvements. Here, in this study, we developed a custom operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) platform that operates under high temperature and steam conditions with applied bias. Quantitative investigations of surface H 2 O/D 2 O isotope exchange in a BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3−δ (BZCYYb1711) protonic electrolyte-based single cell were conducted under different applied voltages using this DRIFTS platform, to gain molecular-level insight into hydration kinetics. The findings show that the application of an external voltage significantly enhances the surface proton exchange rate, decreasing the apparent activation energy from 29.1 kJ mol −1 at open-circuit voltage (OCV) to 6.8 kJ mol −1 at 1.3 V. In addition, distinct voltage-induced spectral shifts in O–D vibrations point to dynamic changes in surface hydration. These findings demonstrate a sensitive spectroscopic platform for probing interfacial proton processes and reveal strong electrochemical control over surface proton kinetics, offering new opportunities for probing electrolyte hydration behavior in PCECs.

36 - MATERIALS SCIENCE↗

Renewable Electrolysis System Development (Final Report)

Renewable hydrogen is becoming globally recognized as a key component required for de-carbonization of our energy system, both as a medium for capture of excess renewable energy sources, vehicle refueling, and as an intermediate for multiple industrial processes. Hydrogen production, via low-temperature electrolysis, is a flexible grid-friendly, clean energy carrying intermediate that enables fast ramp and de-ramp rates as naturally varying solar, wind, and storage systems become a larger percentage of the electricity mix. Analysis shows that by 2050, employing renewable hydrogen at scale can decrease total U.S. CO 2 emissions by about half relative to business as usual, critical to achieving >80% greenhouse gas reduction targets. Energy storage systems help commercial customers reduce their electric bills by storing energy from the grid or from renewable electricity sources when energy is inexpensive, then using that stored energy when demand and prices are high. Proton exchange membrane (PEM) electrolysis is one of the few technologies that can produce hydrogen with zero carbon emissions at relevant scale (hundreds of MWs) in the near term. NREL's research has shown that electrolyzers are fast and flexible enough to participate in energy and ancillary service markets that can help stabilize the grid. In 2015, Proton OnSite (now NEL Hydrogen) introduced the M-series electrolyzer platform, the world's first megawatt PEM electrolyzer for the global energy storage market, offering a carbon-free source of hydrogen fuel or process gas. In addition, the ability to sell the hydrogen into a high value application like vehicle (e.g., light- and heavy-duty and material handling) fueling allows for a layering of revenue streams that creates better business cases for hydrogen energy storage systems (HES). The ability to provide multiple value streams from the fast-responding controllable electrolyzer will have a direct impact on the net cost of hydrogen.

08 HYDROGEN↗

Integrating CO2 Electrolysis with Gas Fermentation to Produce Valuable Fuels and Chemicals

Many industrial activities squander CO2, decreasing process yield. We envision a future where this waste carbon is instead captured, upgraded, and valorized directly at the point of emission. Within the CO2 Reduction and Upgrading Consortium (a collaboration of seven US national laboratories and industrial partners), we are pursuing this goal by developing and de-risking new technologies for low temperature CO2 electrolysis, coupled with biological upgrading of intermediates into more valuable compounds. One such process involves electrocatalytic reduction of CO2 to generate carbon monoxide (CO). As both a carbon and energy source, CO represents an attractive feedstock for microbial upgrading by certain syngas-fermenting species, such as the autotrophic bacterium Clostridium autoethanogenum. Our team has developed new genetic tools and optimized cultivation techniques to enhance C. autoethanogenum as a platform host for the biological conversion of syngas into value-added products. For example, we have created novel CRISPR-based genetic engineering techniques to build new, genome-reduced, platform strains of C. autoethanogenum with improved growth rates. Further, we ve introduced heterologous biochemical pathways into C. autoethanogenum to enable the production of high-value compounds from syngas, such as the isoprenoid precursor mevalonic acid. With the tools of electrochemistry and synthetic biology, there is virtually no limit to the spectrum of products that could be sustainably manufactured from CO2.

09 BIOMASS FUELS↗

Enhancing Oxygen Evolution Reaction and Stability in Proton-Conducting Solid Oxide Electrolysis Cells (p-SOECs) via a Porous Gadolinium-Doped Ceria Interlayer

Proton-conducting solid oxide electrolysis cells (p-SOECs) offer a promising pathway for intermediate temperature (400-600 °C) hydrogen production. However, they still face critical challenges related to sluggish oxygen evolution reaction (OER) kinetics and low Faradaic efficiencies. Here, in this work, we demonstrate that introducing a thin (~0.8 µm) porous Gd 0.1 Ce 0.9 O 1.95 (GDC) interlayer between a BaCo 0.8 Zr 0.1 Zn 0.1 O 3-δ (BCZZ) oxygen electrode and electrolyte significantly enhances p-SOEC performance. The GDC interlayer reduces polarization resistance by 48% (0.54 to 0.28 O cm 2 ) and increases Faradaic efficiency from 63% to 81% at -0.8 A/cm 2 and 600 °C. GDC interlayer p-SOECs display elevated effective H 2 current densities compared to control p-SOECs and reach up to -1.22 A/cm 2 at 1.3 V. Mechanistic studies on the interactions between GDC and BCZZ reveal that GDC intrinsically promotes OER kinetics by significantly reducing the polarization activation energy (Ea p ), dropping from 1.45 to 1.22 eV for full p-SOECs and 0.98 to 0.76 eV for symmetric cells. This promotional effect is localized in the electrochemically active region near the electrolyte interface. Durability testing for over 1500 hours under 50% H 2 O conditions indicates that the GDC interlayer also improves long-term stability, with a degradation rate 53% lower than control p-SOECs. By pinpointing the interfacial region where GDC exerts its promotional effect, highlighting its role in enhancing OER kinetics, and establishing interlayer engineering as a powerful technique, this work provides a unified pathway to simultaneously improve p-SOEC activity, Faradaic efficiency, and durability.

08 - HYDROGEN↗

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr 0.9 Y 0.1 O 3–δ (BPY) vs. Ba 1–x Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ (BCFZY)

Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Active and Resilient Bilayer Oxygen Electrode for Intermediate Temperature Reversible Solid Oxide Cells

High temperature solid oxide cells (SOCs) have intrinsic advantage in efficiency over conventional internal combustion engines for power generation and low-temperature electrolysis cells for H2 production. This efficiency advantage could potentially lead to cost saving and emission reduction. However, commercialization of the current SOCs technology is hindered by its poor durability. One major component with the durability issue is oxygen electrode (OE). For example, the durability of OEs can be negatively affected by the gaseous Cr-species originated from the air oxidation of high-temperature alloy interconnect. For electrolysis operation, on the other hand, delamination of OE from electrolyte, particularly at high current densities, has been identified as a major cause for the performance degradation. Therefore, developing robust and active OEs is of critical importance to SOC technology. WE have previously demonstrated a new bilayer OE with strong activity and stability. Here in this presentation, we present recent results of electrochemical characterization on bilayer OE operating under both fuel cell and electrolysis modes. We will first show the optimization of bilayer OE in terms of thickness, morphology, and calcination temperature and their impacts on cell area specific resistance (ASR). With three-electrode symmetric cell configuration, we also show the results of charge transfer ASR of bilayer OE as a function of current density, temperature, and time in different atmospheres. The results are further compared with the baseline OE (LSCF+GDC) to demonstrate the advantage of bilayer OE.

Huang, Kevin↗

Unlocking the Potential of A-Site Ca-Doped LaCo 0.2 Fe 0.8 O 3-δ : A Redox-Stable Cathode Material Enabling High Current Density in Direct CO 2 Electrolysis

Massive carbon dioxide (CO 2 ) emission from recent human industrialization has affected the global ecosystem and raised great concern for environmental sustainability. The solid oxide electrolysis cell (SOEC) is a promising energy conversion device capable of efficiently converting CO 2 into valuable chemicals using renewable energy sources. However, Sr-containing cathode materials face the challenge of Sr carbonation during CO 2 electrolysis, which greatly affects the energy conversion efficiency and long-term stability. Thus, A-site Ca-doped La1– x CaxCo 0.2 Fe 0.8 O 3-δ (0.2 ≤ x ≤ 0.6) oxides are developed for direct CO 2 conversion to carbon monoxide (CO) in an intermediate-temperature SOEC (IT-SOEC). With a polarization resistance as low as 0.18 O cm 2 in pure CO 2 atmosphere, a remarkable current density of 2.24 A cm –2 was achieved at 1.5 V with La 0.6 Ca 0.4 Co 0.2 Fe 0.8 O 3-δ (LCCF64) as the cathode in La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3-δ (LSGM) electrolyte (300 µm) supported electrolysis cells using La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) as the air electrode at 800 °C. Furthermore, symmetrical cells with LCCF64 as the electrodes also show promising electrolysis performance of 1.78 A cm –2 at 1.5 V at 800 °C. In addition, stable cell performance has been achieved on direct CO 2 electrolysis at an applied constant current of 0.5 A cm –2 at 800 °C. The easily removable carbonate intermediate produced during direct CO 2 electrolysis makes LCCF64 a promising regenerable cathode. The outstanding electrocatalytic performance of the LCCF64 cathode is ascribed to the highly active and stable metal/perovskite interfaces that resulted from the in situ exsolved Co/CoFe nanoparticles and the additional oxygen vacancies originated from the Ca 2 Fe 2 O 5 phase synergistically providing active sites for CO 2 adsorption and electrolysis. Here this study offers a novel approach to design catalysts with high performance for direct CO 2 electrolysis.

30 DIRECT ENERGY CONVERSION↗

Self-sustainable protonic ceramic electrochemical cells using a triple conducting electrode for hydrogen and power production

The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation, highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions, which are the critical steps for both electrolysis and fuel cell operation, especially at reduced temperatures. In this study, a triple conducting oxide of PrNi 0.5 Co 0.5 O 3-δ perovskite is developed as an oxygen electrode, presenting superior electrochemical performance at 400-600°C. More importantly, the self-sustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction, as confirmed by hydrogen permeation experiment, remarkable hydration behavior and computations.

08 HYDROGEN↗

Intermediate Temperature Solid Oxide Cell with a Barrier Layer Free Oxygen Electrode and Phase Inversion Derived Hydrogen Electrode

High-temperature solid oxide cells (SOCs) have fundamental advantages in efficiency and product rate over their low-temperature counterparts. However, the commercial development of SOCs is hindered by cost and reliability. To solve the issues, lowering the operating temperature of SOCs is deemed the best solution. Here we report on our effort toward intermediate temperature (IT) SOCs by developing a barrier layer free high-performance oxygen electrode and open structured hydrogen electrode. The results show that the new oxygen electrode provides reasonably good oxygen electrocatalytic activity at IT range for oxygen reduction and evolution reactions and the open structured hydrogen electrode provides low gas diffusion path for H 2 /H 2 O. However, at high electrolysis current density such as 1 A cm −2 and 650 °C, the present oxygen electrode delaminates after 200 h. The phase-inversion derived open structured hydrogen electrode helps gas diffusion but, in the meantime, reduces reactive sites. A proper balance of porosity and number of reactive sites is still needed for future hydrogen electrode development.

25 ENERGY STORAGE↗

Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.

biomass↗

A highly efficient and durable air electrode for intermediate-temperature reversible solid oxide cells

Solid oxide cells (SOCs) are considered the most efficient system for reversible conversion between chemical and electrical energy, thus having potential to be an attractive technology for a sustainable energy future. To achieve high round-trip efficiency, highly efficient and durable air electrode materials are needed to minimize energy loss associated with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Here we report a bi-functional air electrode material, PrBa 0.9 Co 1.96 Nb 0.04 O 5+δ , demonstrating outstanding electrochemical performance (e.g., achieving peak power densities of over 1.5 and 1 W cm –2 , respectively, for Gd 0.1 Ce 0.9 O 1.95 and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ based fuel cells at 600 °C) while maintaining excellent stability (e.g., having a degradation rate of 40 mV per 1,000 h for H 2 O electrolysis cells). Finally, the excellent property of the new electrode is attributed to the improved stability from Nb doping and the enhanced electrocatalytic activity from tuning Ba deficiency, as confirmed by experimental results and computational analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermochemical processes for CO 2 hydrogenation to fuels and chemicals: Challenges and opportunities

This manuscript discusses the potential use of CO 2 as a carbon and oxygen carrier to return it to the carbon life cycle in the form of fuels or chemicals via thermochemical catalytic pathways. Theoretically, CO 2 hydrogenation can form a variety of fuels and chemicals. Practically, however, the selectivity, conversion, operating range, and kinetic limitations and operational cost determine the end product. Because of their high value and versatility as a chemical or fuel, small olefins (i.e., C 2 H 4 ) and methanol are often considered as target species. Whether alcohol or olefin formation, CH 4 and CO are the nature’s primary choices of CO 2 conversion. They can be formed over a wide operating temperature, pressure, and CO 2 :H 2 ratios. They are often competitive carbon species in olefin or methanol formation steps. Although they are less valuable as end products, they can be used as intermediate species. Secondary processes of CO and CH 4 to form chemicals and fuels can increase the overall CO 2 hydrogenation yield. Independent of the choice of end product, CO 2 hydrogenation requires hydrogen. Pure hydrogen derived mostly from fossil fuels adds to the overall process cost and also increases the CO 2 emissions. Hydrogen produced from water electrolysis is a renewable green pathway but is limited by the process efficiency and cost. As an alternative to pure hydrogen, low-value, small chain paraffins are suggested as the hydrogen carriers. Carbon dioxide–assisted oxidative dehydrogenation of paraffins to olefins process is a direct pathway to olefin formation. The paper discusses these potential pathways for CO 2 utilization based on theoretical analysis and recent advances in academia and industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗